Terminal and internal alkyne complexes and azide-alkyne cycloaddition chemistry of copper(I) supported by a fluorinated bis(pyrazolyl)borate
Autor
Noonikara-Poyil, Anurag
Muñoz-Castro, Álvaro
Dias, H. V.Rasika
Resumen
Copper plays an important role in alkyne coordination chemistry and transformations. This report describes the isolation and full characterization of a thermally stable, copper(I) acetylene complex using a highly fluorinated bis(pyrazolyl)borate ligand support. Details of the related copper(I) complex of HC≡CSiMe3 are also reported. They are three-coordinate copper complexes featuring η2-bound alkynes. Raman data show significant red-shifts in C≡C stretch of [H2B(3,5(CF3)2Pz)2 ]Cu(HC≡CH) and [H2B(3,5-(CF3)2Pz)2 ]Cu(HC≡CSiMe3) relative to those of the corresponding alkynes. Computational analysis using DFT indicates that the Cu(I) alkyne interaction in these molecules is primarily of the electrostatic character. The π-backbonding is the larger component of the orbital contribution to the interaction. The dinuclear complexes such as Cu2 (µ-[3,5(CF3)2Pz])2 (HC≡CH)2 display similar Cu-alkyne bonding features. The mononuclear [H2B(3,5(CF3)2Pz)2 ]Cu(NCMe) complex catalyzes [3 + 2] cycloadditions between tolyl azide and a variety of alkynes including acetylene. It is comparatively less effective than the related trinuclear copper catalyst {µ-[3,5-(CF3)2Pz]Cu}3 involving bridging pyrazolates.
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